DE2121218A1 - Glutamic acid and animal fodder prodn - from carbohydrate -contg materials by fermentation - Google Patents

Abstract

Process for producing animal feedstuffs and glutamic acid comprises (a) hydrolysing a carbohydrate-contg. starting material (e.g. molasses, sugar and/or starch) with an amt. of acid sufficient to give a soln. of pH3.2, (b) filtering the soln. to remove impurities, (c) neutralizing the soln., (d) fermenting the soln. to obtain a broth, (e) separating the broth into a glutamic acid fraction and a waste-broth fraction, and (f) detoxicating the waste-broth fraction to give an animal feedstuff. The problems of disposing of waste broth from glutamic acid are avoided, and the quantities of acid used in the initial hyrolysis are less than those used in conventional glutamic acid prodn. from carbohydrate - contg. starting materials.

Description

Process for the production of feed and glutamic acid At the known fermentation process for the production of glutamic acid is a raw material containing carbohydrates is used, which is hydrolyzed by means of hydrochloric acid and fermented after neutralization. It is then filtered to make a fermentation broth to obtain. The fermentation broth contains glutamic acid. In this procedure However, a large amount of waste broth from which glutamic acid is separated becomes has been discarded. The discarded Waste broth contains relatively large amounts of nutrients, e.g. amino acids, proteins, minerals, vitamins, Fats and sugar residues - However, those in the waste broth are in amounts from 0> 5 Up to 10% ammonium salts contained toxic. Because of this toxicity, the Waste broth discarded. This approach not only leads to a potential loss suitable material, but also brings pollution problems with it, if the waste broth is drained into waterways.

Since the main product of the known processes is glutamic acid, after fermentation the pH of the system under Cl; e maintain to-the proteins to hydrolyze. Hence, large amounts of. Acids, e.g. from hydrochloric acid, are required.

In such known methods it is necessary to have a suitable concentration of hydrochloric acid Maintain about 4 to 5 times the glutamic acid content of the broth is equivalent to. This not only causes a great loss of hydrochloric acid and alkalis, which are needed in the aftertreatment for neutralization, but also brings Corrosion problems with it.

To overcome these disadvantages is therefore according to the invention Process for the production of feed by a fermentation process for In which the glutamic acid is obtained as a by-product.

The method of the invention primarily provides a method for Manufacture of feed for livestock.

However, the process produces both feed and Glutamic acid, and at the same time. Furthermore, the exhaust gases released during the process, e.g. carbon dioxide and ammonia, used to make compounds such as ammonium bicarbonate, Form sodium bicarbonate and ammonium chloride.

The invention is illustrated in more detail in the attached flow chart.

In the method of the invention, molasses or other suitable ones are used Raw materials, e.g. sugar, starch and mixtures of such materials hydrolyzed, in that - as in the known method - an acid is added. In the process of the invention, however, the pH of the solution is adjusted to 3.2, after which with activated charcoal is treated and the whole is filtered to the absorbed To remove dyes and the inorganic impurities. Although with that Processes of the invention all normally employed in the known processes Acids can be used, but here are hydrochloric acid and sulfuric acid preferred. This treatment takes place before fermentation at a pH of 3.2. In a conventional method, most of the coloring and the inorganic impurities during fermentation because of the pH of the system is adjusted to 6.0 to 7.0 and because the impurities in this pH range are soluble.

According to the present invention, that is obtained after filtration The filtrate was neutralized by adding ammonia. In one embodiment of the invention becomes the required amount of ammonia from a concentration operation after detached from fermentation and returned to this stage. This feature will described below, the ammonia required for fermentation is returned from the detox stage.

According to the invention, the waste broth from which the glutamic acid has been separated, detoxified to make the feed. This detox stage includes the addition of calcium salts or calcium salts, some of which are mixed with sodium, Potassium or magnesium salts are mixed in. These salts enable the drain a {substitution reaction with the ammonium salts in the broth.

The ammonia is removed by distilling the waste broth, which is partly returned to the fermentation plant and partly in an exhaust gas recovery stage is won. The liquid feed obtained can be further filled with hay powder and mixed with it thoroughly. It can also be subjected to spray crystallization to become a solid or pelletized feed.

That happens during the fermentation of the broth and / or the conversion of the glutamic acid Carbon dioxide released to form monosodium glutamate and the ammonia from the detoxification stage are recovered and converted to sodium bicarbonate, ammonium bicarbonate, ammonium chloride and to form other desired by-products. The sodium bicarbonate obtained can can be further utilized in order to react with the glutamic acid to the formation of monosodium glutamate monohydrate to be implemented.

In the plant described in the flow diagram, the raw material M, e.g. a molasses, diluted with water and well done Adding one Acid hydrolyzed in stage 1. The pH of the hydrolyzed solution is increased to 3.2 set and the solution is treated with activated charcoal and in stage 2 filtered to remove coloring matter and inorganic impurities. While the filtration, the pH is kept at 3.2.

The filtrate leaving stage 2 is mixed with ammonia from the source 9 (which will be described below) is neutralized and the filtrate and ammonia become brought into the fermentation tank 3. The fermentation in the tank 3 takes place in the same way as in the known method, except that the impurities removed prior to fermentation in the manner described above. ammonia and other means necessary for fermentation are drawn from the tank N introduced into the fermentation tank. The fermentation broth FB, which after the Fermentation obtained in stage 3 is divided into two roughly equal fractions split, one of which in stage 9 of a treatment to remove the dissolved Ammonia AM1 is subjected. The ammonia can be recycled to neutralization of the filtrate in stage 3 as described above. The one in the stage 9 concentrated solution obtained is introduced into a crystallization stage 11, after being treated in step 10 with a glutamic acid solution GA2 (as described below) has been mixed. The crystalline melt is produced from the crystallization stage 11 discharged and separated to obtain glutamic acid GA1- as a by-product. The mother liquor GL is combined with the second fraction of the fermentation broth. The pH of the combined mixture of the mother liquor and the fermentation broth is set to 5.0 to avoid the formation of coloring matter to inhibit. The combined mixture then undergoes a step 4 concentration treatment and in stage 5 by adding an acid A, e.g. hydrochloric acid or Sulfuric acid, neutralized. The mixture is then filtered to obtain an intermediate glutamic acid GA2, which is subsequently dissolved by the acid A in stage 6 and is treated with activated carbon in step 7 in order to remove the by-waste product LW. The pH of the resulting solution of glutamic acid GA2 is set to 0.5 in stage 8 set before it is introduced into the mixing zone 10. The waste broth WB, which is separated from the intermediate glutamic acid G, A2, is detoxified to how described below to produce a feed.

The crude glutamic acid from mixing stage 10 is treated by treatment cleaned and bleached with activated charcoal and sodium sulfite. Certain dyes, such as flavin and riboflavin cannot be completely absorbed by the activated carbon will. However, the recrystallization of the product of the crystallization stage 11 can be used to reduce the content of such dyes. Further can pyrrolidonization and racemization by recrystallization of glutamic acid can be avoided, so that a greater yield of a qualitative high quality glutamic acid by-product can be obtained.

According to the invention, during the crystallization of the glutamic acid Oxalic acid added to remove trace amounts of potassium salts. The calcium oxalate formed is then dissolved using an Idelta chelating agent is added.

During the crystallization of glutamic acid, the ratio should Glutamic acid to the water content in the entire system below 23: 100, preferably be below 20: 100 to allow the growth of large glutamic acid crystals that can be easily cleaned and separated.

The Abrallbrähe WB is detoxified in stage 21 by containing calcium Substances C, e.g. calcium oxide, calcium hydroxide or oyster shell powder added to cause a substitution reaction which gives an ammonium salt. The calcium-containing substances C can also be made up of sodium, potassium or magnesium compounds replaced or partially mixed with it. The remaining excess on Ammonia is separated in the distillation stage 22, which is a steam distillation, a vacuum distillation or a normal thermal distillation at normal pressure may include. The ammonia gas AM2> that is released is extracted to make sodium bicarbonate and the like, as described below, or it is dissolved in water, to make ammonia water.

After the distillation, the broth is made by adding a suitable Acid neutralized to form a liquid feed FF. The liquid feed FF can be mixed with hay powder P, e.g. sugar cane leaves, bagasse, banana tree bodies or Corn stalks are mixed and. be spray crystallized in step 23 to as Main product of the process to manufacture solid, pellet-shaped feed SF.

The carbon dioxide gases CD1 and CD2 emanating from the fermentation stage 3 and the sodium glutamate formation stage 33 are released in stage 31 cleaned in a known manner, then pressurized and implemented in stage 34 with ammonia AM2. The latter becomes from the distillation stage 22 and then in the cleaning stage 35 and in the absorption stage 36 treated by means of the mother liquor BL. The product from reaction stage 34 is filtered in the filtration stage 37 to ammonium bicarbonate AB and mother liquor BL to obtain, which is returned to the reaction stage 34 to ammonia AM2 to absorb.

If sodium bicarbonate is preferred instead of ammonium bicarbonate, then some of the purified ammonia AM2 is introduced into the mother liquor in stage 38 in order to convert all of the bicarbonate ions present therein and to form ammonium carbonate in this stage. After cooling in stage 39 and separation in stage 40, ammonium chloride AC is obtained from the system. The mother liquor CL is used to dissolve this salt in the stage 32 and it is returned to the absorption stage 36 in order to absorb the purified ammonia AM2 in order to introduce this into the reaction stage 34 and there the course of a reaction between the carbon dioxide, the Allow sodium chloride, ammonia and water to form sodium carbonate SB. This is done according to the equation The amount of sodium bicarbonate is sufficient to react with the glutamic acid GA1 obtained in the step 33, whereby the monosodium glutamate monohydrate MSG is obtained. The carbon dioxide CD2 released during reaction 33 is recovered. The sodium bicarbonate SB obtained can be mixed with the glutamic acid GA1 to produce a seasoning and foaming agent for the feed.

The invention is illustrated in the examples.

Example 1 3.7 kg of molasses are diluted with water and added hydrolyzed by 7.5 g of sulfuric acid. After settling out the impurities will the pH is adjusted to 3.2 by adding a sufficient amount of calcium oxide. The solution is stirred with 0.08 kg of activated charcoal and filtered off.

The filtrate is neutralized by the recycled ammonia and brought into the fermentation tank together with the known fermentation agents.

18.0 kg of fermentation broth are obtained, which is divided into two fractions is divided. The first fraction of 8.8 kg is used to remove the contained therein Ammonia is distilled, and concentrated to 4.4 kg, making the concentrated broth No. 1 is obtained. The second fraction of 9,? kg becomes with 9.46 kg mother liquor and a washing solution of the intermediate glutamic acid having a glutamic acid content of 0.44 kg mixed. This broth is concentrated to 3.75 kg, making the concentrated Broth No. 2 is obtained.

The resulting concentrated broth No. 2 is thoroughly 6 kg of one Recirculated filtrate and stirred by Zugbe of enough hydrochloric acid at a Temperature adjusted from 35 ° C to a pH of 3.2. After detaching and Washing is carried out with 0.85 kg of an intermediate glutamic acid with inclusion of 21.3% water and 0.8% ammonium chloride and 9.6 kg of filtrate and 0.44 kg of washing solution were obtained.

6.0 kg of the filtrate are used together with the washing solution returned while 3.6 kg of residues filtered waste broth treated to produce a feed.

The 0.85 kg of intermediate glutamic acid are added by adding 0.528 kg hydrochloric acid adjusted to a pH of 0> 5.

The mixture is then thoroughly stirred with 0.08 kg of activated charcoal and filtered off and washed. The filtrate and the washing solution give when combined 5.6 kg, including 0.67 kg of glutamic acid.

The combined mixture is mixed with the # 1 concentrated broth and adjusted to a pH of 3> 2 at a temperature of 320C. ',' After cooling, filtering and washing are 1.1 kg of glutamic acid by-product, the Contains 10% water, 0.14% ammonium chloride and 0.014% calcium sulfate, as well as 9t46 kg mother liquor obtained. The yield of glutamic acid, based on the fermentation broth, is 92 t 2%.

Example 2 The 1.1 kg of glutamic acid from Example 1 are with 1.35 kg of water diluted. The pH is adjusted by adding a sufficient amount of sodium bicarbonate set to 6.0.

It is with 0.08 kg of a 25% aqueous suspension of activated charcoal mixed and the pH is readjusted to 6.5 with sodium bicarbonate. About 5 cm3 of oxalic acid are added until the filtrate has a pH of 6.8 to 7.0. Then 5 cm3 of sodium sulfide are added and the pH value becomes adjusted to 7> 0 and it is filtered. 2.5 liters of the filtrate of monosodium glutamate will together with the washing solution, which has a density of 1.2 at 45 ° C, into one Crystallizer transferred after adding 0.5 cm3 of an Idelta chelating agent have been.

The analysis of the obtained monosodium glutamate showed the following contents: NH4C1 80 ppm - 300 ppm max.

Idelta 6 ppm - 100 ppm max.

Ca ++ 0.3 ppm - 4 ppm max.

Example 3 The 1.0 kg of waste broth obtained in the process according to Example 1 obtained are treated with 0.12 kg of calcium hydroxide. The system is heated to 80 + 5 ° C and distilled at a pressure of 600 t 50 mm Hg to To remove the ammonia contained in it, the broth desorbed by ammonia becomes neutralized by adding 6.5 cm3 of hydrochloric acid. This way it will be 1.1 kg get liquid feed.

The composition of the waste broth and liquid feed of Example 3 is given in Table 1.

Table 1 Waste liquid broth feed -pH 3> 2 6.8 Be 23 / 360C 23.5 / 25 ° C total glutamic acid, wt% 3.52 3.2 total sugars, wt% 3.78 3> 44 ammonium chloride,% by weight 6.8 0.015 amino acids,% by weight 8.7 8, o crude protein, % By weight 5.9 5.23 calcium chloride,% by weight --- 7.94 cell volume 16.8 remainder 71.3 72.175 (including organic acids, minerals, vitamins, antibiotics and water) Using the liquid feed of Example 3, the following was made Way, a feeding experiment was carried out.

Biological experiment A) animals: guinea pigs B) feed composition, parts by weight Example 3: Liquid feed: 1 part mixed Rice twigs: 1 part Dried banana tree powder: 2 parts Rice flour: 1 part Comparison 1: Waste broth: 1 part Dried banana tree powder: 2 parts Rice flour: 1 part comparison 2: Mixed rice branches: 1 part dried banana tree powder: 2 parts rice flour: 1 part Sufficient water and salt are provided for Sede Gruppe.

c) 60 days. each guinea pig will be on once for 18 days Weighed the day, then once a week until the end of the experiment. The received The results are shown in Table 2.

Table 2 Results of the biological experiment Example 3 Comparison 1 comparison 2 days no. No. No. No. No. No. No. No. No. No. No. No. No. No. No.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 150 140 162 135 154 152 153 145 147 156 145 147 155 141 155 2 150 140 162 135 155 -145 153 142 147 156 145 147 155 141 155 3 150 140 161 134 155 130 151 140 146 155 145 147 156 142 156 4 151 140 161 135 154 + 149 138 144 152 146 147 156 142 157 5 151 141 161 135-154 148 130 140 145 146 147 157 143 157 6 150 141 160 136.155 145 + + 143 146 148 157 143 157 7 152 140 161.136-155 141 140 146 148 158 143 158 8 152 141 i62 136 156 138 136 147 148 158 143 158 9 155-142-163 137 156 135 133 147 148 158 143 159 10 153 i42 164 137 157 131 131 147 149 158 143 159 11 153 142 165 137 158 135 126 148 150 158 144 159 12 154 143 166 138 158 + 121 148 150 159 145 159 13 154 144 167 139 159 + 149 151 159 145 160 14 155 145 168 140 160 149 151 160 146 161 15 156 146 169 141 161 150 152 161 146 161 16 157 147 170 142 162 151 152 161 146 162 17 159 159 171 143 163 151 153 162 146 163 18 160 159 172 145 165 152 153 162 147 163 25 170 165 180 163 173 158 165.171 156 169 32 177 175 187 175 181 164 168 177 162 17 39 185 184 190 181 189 172 175 180 165 18O 46 198 194 218 198 199 179 182 196 175 185 52 232 221 239 227 237 187 189 192 181 191 60 240 241 251 241 253 190 193 201 184 198 + = death due to acidosis

Claims (12)

Claims 1. Process for the production of animal feed and Glutamic acid through a fermentation process from a carbohydrate-containing material, by: a) the carbohydrate-containing raw material with enough acid to give a solution with a pH of 3.2, hydrolyzed, b) the solution is filtered to remove the impurities, c) the Solution neutralizes, d) the solution is fermented to obtain a fermentation broth, e) the fermentation broth into a glutamic acid fraction and a waste broth fraction separates, and that f) the waste stock fraction for the production of a feed detoxifies. 2. The method according to claim 1, characterized in that g e k e n n -z e i c h n e t that one uses molasses sugar and / or starch as the carbohydrate-containing material. 3, method according to claim 1 or 2, characterized in that g e k e n n -z e i c n e t that before fermentation the hydrolyzed carbohydrate material with Treated activated carbon. 4. The method according to any one of claims 1 to 3, characterized g e k e n n notices that the filtrate is neutralized with ammonia. 5. The method according to any one of claims 1 to 4, characterized g e k e n n z e i c h n e t that the carbon dioxide formed during the process and Ammonia wins and converts it to ammonium bicarbonate. 6. The method according to any one of claims 1 to 4, characterized g e k e n n z e i c h n e t that the carbon dioxide formed during the process and Ammonia wins and with sodium chloride to sodium bicarbonate and ammonium chloride implements. 7. The method according to any one of claims 1 to 6, characterized in that g e k e n n indicates that the carbohydrate raw material can be mixed with an acid from the group Hydrochloric acid and sulfuric acid hydrolyzed. 8. The method according to any one of claims 1 to 7, characterized g e k e n n indicates that the animal feed obtained is mixed with hay powder. 9. The method according to any one of claims 1 to 8, characterized g e k e n n notices that the waste liquor can be removed by removing what it contains Ammonia detoxifies. 10. The method according to any one of claims 1 to 8, characterized g e k e n It does not point out that one detoxifies the waste broth in such a way that one can use it reacts with a calcium salt. 11. The method according to claim 10, characterized in that g e k e n n -z e i c h n e t that the calelum salt is mixed with a sodium, potassium and / or magnesium salt. 12. The method according to any one of claims 1 to 9; as a result N e i c e n e t that one detoxifies the waste broth by removing what is in it Removed ammonia and the removed ammonia to neutralize the filtered recirculates hydrolyzed solution. L e r s e i t e